CN113348216B - Radiation curable inkjet inks for interior decoration - Google Patents
Radiation curable inkjet inks for interior decoration Download PDFInfo
- Publication number
- CN113348216B CN113348216B CN202080010695.5A CN202080010695A CN113348216B CN 113348216 B CN113348216 B CN 113348216B CN 202080010695 A CN202080010695 A CN 202080010695A CN 113348216 B CN113348216 B CN 113348216B
- Authority
- CN
- China
- Prior art keywords
- group
- radiation curable
- curable inkjet
- inkjet ink
- acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J11/00—Devices or arrangements of selective printing mechanisms, e.g. ink-jet printers or thermal printers, for supporting or handling copy material in sheet or web form
- B41J11/0015—Devices or arrangements of selective printing mechanisms, e.g. ink-jet printers or thermal printers, for supporting or handling copy material in sheet or web form for treating before, during or after printing or for uniform coating or laminating the copy material before or after printing
- B41J11/002—Curing or drying the ink on the copy materials, e.g. by heating or irradiating
- B41J11/0021—Curing or drying the ink on the copy materials, e.g. by heating or irradiating using irradiation
- B41J11/00214—Curing or drying the ink on the copy materials, e.g. by heating or irradiating using irradiation using UV radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/0023—Digital printing methods characterised by the inks used
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
- E04F13/00—Coverings or linings, e.g. for walls or ceilings
- E04F13/002—Coverings or linings, e.g. for walls or ceilings made of webs, e.g. of fabrics, or wallpaper, used as coverings or linings
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
- E04F13/00—Coverings or linings, e.g. for walls or ceilings
- E04F13/07—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor
- E04F13/08—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements
- E04F13/0871—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements having an ornamental or specially shaped visible surface
-
- E—FIXED CONSTRUCTIONS
- E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
- E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
- E06B3/00—Window sashes, door leaves, or like elements for closing wall or like openings; Layout of fixed or moving closures, e.g. windows in wall or like openings; Features of rigidly-mounted outer frames relating to the mounting of wing frames
- E06B3/70—Door leaves
- E06B3/7001—Coverings therefor; Door leaves imitating traditional raised panel doors, e.g. engraved or embossed surfaces, with trim strips applied to the surfaces
Abstract
A radiation curable inkjet ink comprising a polymerizable compound comprising a vinyl ether group or a vinyl amide group; optionally, an amine synergist comprising an alkanolamine group or a dimethylbenzoate group; optionally, a Norrish type II photoinitiator comprising a photoinitiating moiety selected from the group consisting of a thioxanthone group, a benzophenone group, a ketocoumarin group, and a camphorquinone group; and a specific singlet oxygen quencher.
Description
Technical Field
The present invention relates to radiation curable inkjet inks, in particular UV curable inkjet inks for the manufacture of decorative articles for interior decoration.
Background
Inkjet printing systems are added to industrial production lines due to their enhanced reliability. The main advantage of ink jet is that it provides a high degree of flexibility, for example variable data printing allows small run lengths, even single prints, without extensive pre-press preparation. Radiation curable inkjet inks are particularly preferred because high quality images can also be printed on non-absorbing ink receivers, especially when the inkjet ink contains no or low amounts of volatile organic solvents or water.
A typical characteristic of an inkjet ink is that it must have a very low viscosity, for example 5 to 15mpa.s at the printing temperature, in order to be able to eject in small droplets with a volume in the picoliter range. To achieve these low viscosity values, radiation curable inks must contain very high levels of reactive diluents. These reactive diluents having low viscosity generally exhibit low radiation curing reactivity, which may lead to skin irritation problems if the cured layer is in contact with human skin. The latter is not acceptable for interior decoration where health risks must be minimized.
So-called low-migration radiation curable inkjet inks have been designed for food packaging applications. For example, EP2053101A (AGFA) discloses curable inkjet inks having very low amounts of extractable monomers and photoinitiators by using mixed monomers having two different types of polymerizable groups, e.g. acrylate groups and vinyl ether groups. However, it has been observed that while vinyl ether compounds are very effective in reducing the viscosity and migrateable mass of inkjet inks, they are susceptible to hydrolysis to form aldehydes under certain UV curing conditions.
These aldehydes are associated with health risks, such as formaldehyde associated with an excessive risk of nasopharyngeal and other cancers. One way to avoid aldehyde formation is to add hydrolysis stabilizers. For example, US20030083396A (3M) discloses carbodiimide compounds such as Stapoxol from Rhein Chemie Corporation TM Use of I in a radiation curable inkjet ink. However, these commercial compounds have not been found to work well in all cases and often lead to other problems, such as reduced shelf life.
Thus, there is still a need for radiation curable inkjet inks, in particular UV curable inkjet inks for interior decoration applications, which result in low health risks caused by aldehydes, while other properties (such as low viscosity or shelf life) are not compromised.
Summary of The Invention
To overcome the above problems, a preferred embodiment of the present invention has been achieved with a radiation curable inkjet ink as defined in claim 1.
It has surprisingly been found that specific singlet oxygen quenchers are able to reduce health risks caused by aldehydes upon UV exposure of layers made from radiation curable inkjet inks comprising polymerizable vinyl ether or vinyl amide compounds, especially in the presence of Norrish type II photoinitiators selected from thioxanthones and benzophenones. These specific singlet oxygen quenchers allow for the preparation of inkjet inks with good shelf-life stability.
These and other objects will become apparent from the detailed description below.
Description of the embodiments
Definition of
The term "radiation curable" as used in radiation curable inkjet inks means that the inkjet inks can be cured by actinic radiation, such as UV radiation and electron beams, preferably UV radiation. The latter inkjet inks are also referred to as UV curable inkjet inks.
The term "monofunctional", as used for monofunctional polymerizable compounds, refers to polymerizable compounds that contain a single polymerizable group.
The term "multifunctional", as used for multifunctional polymerizable compounds, refers to polymerizable compounds containing two, three, or more polymerizable groups.
The term "alkyl" refers to all possible variations of the number of carbon atoms in the alkyl group, i.e. methyl, ethyl, for three carbon atoms: n-propyl and isopropyl; for four carbon atoms: n-butyl, isobutyl, and tert-butyl; for five carbon atoms: n-pentyl, 1-dimethyl-propyl, 2-dimethylpropyl, and 2-methyl-butyl, and the like. This applies in an analogous manner also to alkenyl, alkynyl, alkylaryl and arylalkyl groups.
The term "substituted", for example in a substituted alkyl group, means that the alkyl group may be substituted with atoms other than those typically present in the group (i.e., carbon and hydrogen). For example, a substituted alkyl group may include a halogen atom or a thiol group. Unsubstituted alkyl groups contain only carbon and hydrogen atoms.
Unless otherwise specified, substituted alkyl, substituted alkenyl, substituted alkynyl, substituted aralkyl, substituted alkaryl, substituted aryl, and substituted heteroaryl groups are preferably substituted with one or more substituents selected from the group consisting of esters, amides, ethers, thioethers, ketones, aldehydes, sulfoxides, sulfones, sulfonic acidsEsters, sulfonamides, -Cl, -Br, -I, -OH, -SH, -CN and-NO 2 Partial substitution of (a).
Unless otherwise specified, substituted or unsubstituted alkyl is preferably C 1 To C 6 An alkyl group.
Unless otherwise specified, substituted or unsubstituted alkenyl is preferably C 2 To C 6 An alkenyl group.
Unless otherwise specified, substituted or unsubstituted alkynyl is preferably C 2 To C 6 Alkynyl.
Unless otherwise specified, a substituted or unsubstituted aralkyl group preferably includes one, two, three or more C 1 To C 6 Alkyl phenyl or naphthyl.
Unless otherwise specified, a substituted or unsubstituted alkaryl group is preferably C comprising a phenyl or naphthyl group 7 To C 25 An alkyl group.
Cyclic groups include at least one ring structure and may be monocyclic or polycyclic groups, the latter meaning that one or more rings are fused together.
Heterocyclic groups are cyclic groups having at least two atoms of different elements as ring members. The counterpart of a heterocyclic group is a carbocyclic group, the ring structure of which consists of carbon only. Unless otherwise specified, a substituted or unsubstituted heterocyclic group is preferably a five-or six-membered ring substituted with one, two, three or four heteroatoms, preferably selected from an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom or a combination thereof.
Alicyclic groups are non-aromatic carbocyclic groups in which the ring atoms consist of carbon atoms.
The term heteroaryl refers to a monocyclic or polycyclic aromatic ring comprising carbon atoms and one or more heteroatoms, preferably 1 to 4 heteroatoms independently selected from nitrogen, oxygen, selenium and sulfur, in the ring structure. Preferred examples of heteroaryl groups include, but are not limited to, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, pyrrolyl, pyrazolyl, imidazolyl, (1,2, 3') -and (1,2,4) -triazolyl, pyrazinyl, pyrimidinyl, tetrazolyl, furanyl, thienyl, isoxazolyl, thiazolyl, isoxazolyl, and oxazolyl. Heteroaryl groups may be unsubstituted or substituted with one, two or more suitable substituents. Preferably, the heteroaryl group is a monocyclic ring, wherein the ring comprises 1 to 5 carbon atoms and 1 to 4 heteroatoms. More preferably, the substituted or unsubstituted heteroaryl group is preferably a five-or six-membered ring substituted with one, two or three oxygen atoms, nitrogen atoms, sulfur atoms, selenium atoms, or a combination thereof.
Unless otherwise specified, unsubstituted aryl is preferably phenyl or naphthyl.
Unless otherwise specified, acyl is preferably a-C (= O) -R group, wherein R is selected from optionally substituted alkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkaryl and optionally substituted aralkyl.
The acyl group in the present invention is preferably a benzoyl group such as a 2, 6-dimethylbenzoyl group, a 2, 6-dimethoxybenzoyl group or a 2,4, 6-trimethylbenzoyl group.
Radiation curable inkjet inks
In a preferred embodiment of the present invention, the radiation curable inkjet ink comprises a polymerizable compound comprising a vinyl ether group or a vinyl amide group; optionally, an amine synergist comprising an alkanolamine group or a dimethylbenzoate group; optionally, a Norrish type II photoinitiator comprising a photoinitiating moiety selected from the group consisting of a thioxanthone group, a benzophenone group, a ketocoumarin group, and a camphorquinone group; and a singlet oxygen quencher according to formula (I):
wherein
The integer N =0 if X represents S, or N =1 if X represents N;
r1 and R2 represent independently selected C 1 -C 6 Alkyl groups of alkyl groups; r3 represents C 1 -C 6 Alkyl or a-L4- (C = O) -O-R5 group;
r4 represents C 1 -C 6 Alkyl or a-L5- (C = O) -O-R6 group;
l1 to L5 represent alkylene groups independently selected from ethylene, propylene and butylene groups; and
r5 and R6 represent independently selected C 1 -C 6 Alkyl groups of the alkyl groups.
The radiation curable inkjet ink may be a colourless radiation curable inkjet ink, but preferably it comprises a colorant. The colorless radiation curable inkjet ink can be used, for example, as a primer to improve adhesion to a substrate or as a varnish to improve gloss of an image.
For printing multicolor images, the radiation curable inkjet ink is part of a radiation curable inkjet ink set. A preferred radiation curable inkjet ink set for printing different colors comprises at least two or three but most preferably at least four radiation curable inkjet inks according to the present invention. The inkjet ink set is preferably a radiation curable CMYK or CRYK inkjet ink set, preferably further comprising a radiation curable white inkjet ink to enhance colour vibrancy. The inkjet ink set may also be extended with additional inks, such as violet, green, red, blue, and/or orange, to further expand the gamut of the image. The radiation curable inkjet ink set can also be extended by the combination of full density inkjet inks with light density inkjet inks. The combination of dark and light inks and/or black and gray inks improves image quality by reducing graininess.
In a preferred embodiment, the radiation curable inkjet ink comprises the organic colour pigment in a preferred amount of 0.1 to 13.0 wt. -%, more preferably 1.0 to 10.0 wt. -%, most preferably 2.0 to 8.0 wt. -%, based on the total weight of the radiation curable inkjet ink. Within the above range, the color gamut is maximized.
For light density color inkjet inks, the organic color pigment is preferably present in an amount of from 0.1 to 1.0 wt%, preferably from 0.2 to 0.9 wt%, more preferably from 0.3 to 0.5 wt%, based on the total weight of the radiation curable inkjet ink. Within the above range, the graininess in the printed image is minimized.
The radiation curable inkjet ink preferably comprises 60 to 95 wt% of polymerizable compounds, more preferably 70 to 90 wt% of polymerizable compounds, based on the total weight of the radiation curable inkjet ink. The varnish may comprise up to 99 wt% of polymerizable compounds based on the total weight of the radiation curable inkjet ink.
In order to have good jetting ability, 1000s -1 And a jetting temperature of from 30 to 70 ℃, preferably at a temperature of 45 ℃, the viscosity of the radiation curable inkjet ink at the jetting temperature is preferably less than 30.0mpa.s, more preferably less than 20.0mpa.s, most preferably from 5.0 to 16.0mpa.s, or even from 8.0 to 15.0 mpa.s.
The surface tension of the radiation curable inkjet ink is preferably in the range of 20 to 35mN/m at 25 ℃, more preferably in the range of about 22 to about 30mN/m at 25 ℃. Within these ranges, good ink spreading is obtained over a wide range of substrates.
The radiation curable inkjet ink may further comprise at least one polymerization inhibitor for improving the thermal stability of the ink.
The radiation curable inkjet ink may further comprise at least one surfactant for obtaining good spreading characteristics on the substrate.
There is no limitation to combine any of the above preferred embodiments with each other.
Singlet oxygen quenchers
The singlet oxygen quenchers used in the invention are preferably compounds according to formula (I):
wherein
The integer N =0 if X represents S, or N =1 if X represents N;
r1 and R2 represent independently selected C 1 -C 6 Alkyl groups of alkyl groups; r3 represents C 1 -C 6 Alkyl or a-L4- (C = O) -O-R5 group;
r4 represents C 1 -C 6 Alkyl or a-L5- (C = O) -O-R6 group;
l1 to L5 represent alkylene groups independently selected from ethylene, propylene and butylene groups; and
r5 and R6 represent independently selected C 1 -C 6 Alkyl groups of the alkyl groups.
In a more preferred embodiment of the singlet oxygen quencher, L1 to L5 represent ethylene.
In another more preferred embodiment of the singlet oxygen quencher, R1 to R6 represent ethyl.
The above two more preferred embodiments may be combined.
The singlet oxygen quencher is preferably a compound selected from HS-1 to HS-4 in Table 1.
TABLE 1
Singlet oxygen quenchers according to the invention may be used alone or in combination.
The synthesis of these singlet oxygen quenchers is within the routine skill of those in the art of synthetic organic chemistry and is exemplified in example 1 below.
Polymerizable compounds comprising vinyl ether or vinyl amide groups
The polymerizable compound comprising a vinyl ether may be a monofunctional or a multifunctional polymerizable compound.
Preferred examples of monofunctional polymerizable compounds including vinyl ethers are ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol monovinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, isopropenyl vinyl ether, dodecyl vinyl ether, ethylene glycol monovinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, octadecyl vinyl ether, hydroxyethyl monovinyl ether, and hydroxynonyl monovinyl ether.
Preferred examples of the polyfunctional polymerizable compound including vinyl ether are ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, and trimethylolpropane trivinyl ether. Among them, triethylene glycol divinyl ether is particularly preferable because of good storage stability.
The polymerizable compound comprising a vinyl ether may also be a multifunctional polymerizable compound having different types of polymerizable groups, preferably a vinyl ether group and a radical polymerizable group selected from acrylate, methacrylate, acrylamide and methacrylamide. More preferred for the one or more free radically polymerizable groups are acrylates and methacrylates, with acrylates being most preferred.
Particularly preferred polymerizable compounds including vinyl ethers are represented by the formula (VA-1):
CH2= CR1-COO-R2-O-CH = CH-R3 formula (VA-1)
Wherein R1 is a hydrogen atom or a methyl group, R2 is a divalent organic residue having 2 to 20 carbon atoms, and R3 is a hydrogen atom or a monovalent organic residue having 1 to 11 carbon atoms. Preferably, the divalent chain of R2 of 2 to 20 carbon atoms is optionally interrupted by one or more oxygen atoms. Preferably, R2 is a divalent chain of 2 to 20 carbon atoms optionally interrupted by one or more oxygen atoms.
In a preferred embodiment of the compounds according to formula (VA-1), R1 and R3 represent hydrogen.
In a more preferred embodiment of the compounds of formula (VA-1), R1 and R3 represent hydrogen and R2 represents a divalent chain of 2 to 20 carbon atoms optionally interrupted by one or more oxygen atoms.
Suitable examples of compounds of formula (VA-1) include, but are not limited to, 2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, 1-methyl-2-vinyloxyethyl (meth) acrylate, 2-vinyloxypropyl (meth) acrylate, 4-vinyloxybutyl (meth) acrylate, 1-methyl-3-vinyloxypropyl (meth) acrylate, 1-vinyloxymethylpropyl (meth) acrylate, 2-methyl-3-vinyloxypropyl (meth) acrylate, 1-dimethyl-2-vinyloxyethyl (meth) acrylate, 3-vinyloxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl acrylate, methyl acrylate, ethyl acrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 1-methyl-2-vinyloxypropyl (meth) acrylate, 2-vinyloxybutyl (meth) acrylate, 4-vinyloxycyclohexyl (meth) acrylate, 6-vinyloxyhexyl (meth) acrylate, 4-vinyloxymethylcyclohexyl (meth) acrylate, 3-vinyloxymethylcyclohexyl methyl (meth) acrylate, 2-vinyloxymethylcyclohexyl methyl (meth) acrylate, vinyloxymethylphenyl methyl (meth) acrylate, m-vinyloxymethylphenyl methyl (meth) acrylate, o-vinyloxymethylphenyl methyl (meth) acrylate, 2- (2-vinyloxyethoxy) ethyl methacrylate, 2- (2-vinyloxyethoxy) ethyl acrylate (VEEA), 2- (vinyloxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxy) propyl (meth) acrylate, 2- (vinyloxyethoxy) isopropyl (meth) acrylate, 2- (vinyloxyisopropoxy) propyl (meth) acrylate, 2- (vinyloxyisopropoxy) isopropyl (meth) acrylate, 2- (vinyloxyethoxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyethoisoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxyisopropoxyisopropoxyisopropoxyisopropoxyisopropoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyethoxy) propyl (meth) acrylate, 2- (vinyloxyethoxyethoxyethoxyethoxy) propyl (meth) acrylate, 2- (vinyloxyethoxyethoxy) propyl (meth) acrylate, 2- (vinyloxyethoxy) isopropyl (meth) acrylate, 2- (vinyloxyethoxy) propyl (meth) acrylate, 2- (vinyloxyethoxy) isopropyl (meth) acrylate, 2- (vinyloxyethoxy) ethyl (meth) acrylate, 2- (vinyloxy) acrylate, 2- (vinyloxyethoxy) acrylate, 2- (vinyloxy) isopropyl (meth) acrylate, 2, and (meth) acrylate, 2, and (meth) acrylate, 2, or (meth) acrylate, or a mixture thereof, or a mixture of, 2- (vinyloxyethoxyethoisopropoxy) propyl (meth) acrylate, 2- (vinyloxyethoisopropoxy ethoxy) propyl (meth) acrylate, 2- (vinyloxyethoisopropoxy isopropoxy) propyl (meth) acrylate, 2- (vinyloxyethoxyethoxyethoxy) isopropyl (meth) acrylate, 2- (vinyloxyethoisopropoxy isopropoxy) isopropyl (meth) acrylate, 2- (vinyloxyethoisopropoxy ethoxy) isopropyl (meth) acrylate, 2- (vinyloxyethoisopropoxy isopropoxy) isopropyl (meth) acrylate, 2- (vinyloxyethoxyethoxyethoxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyethoxyethoxyethoxyethoxyethoxyethoxyethoxyethoxyethoxyethoxyethoxyethoxyethoxyethoxyethoxyethoxyethoxyethoxy) ethyl (meth) acrylate, a polymer having a high degree of polymerization, 2- (isopropenyloxyethoxy) ethyl (meth) acrylate, 2- (isopropenyloxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2- (isopropenyloxyethoxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2- (isopropenyloxyethoxyethoxyethoxyethoxyethoxyethoxyethoxyethoxy) ethyl (meth) acrylate, polyethylene glycol monovinyl ether (meth) acrylate and polypropylene glycol monovinyl ether (meth) acrylate.
2- (2-Vinyloxyethoxy) ethyl acrylate is particularly preferred in the above examples because it is advantageous to provide a good balance between the curability and viscosity of the radiation curable inkjet ink.
The polymerizable compound containing a vinylamide group is preferably a cyclic compound represented by the formula (NV-1):
wherein n represents an integer of 2 to 6, n is preferably 3 or 5, and n is particularly preferably 5. Such compounds are also known as N-vinyllactams. The N-vinyl lactam may have a substituent such as an alkyl group or an aryl group on the lactam ring, and may have a saturated or unsaturated ring structure bonded to the lactam ring.
Particularly preferred polymerizable compounds comprising vinylamides are N-vinylcaprolactam and N-vinyl-2-pyrrolidone. Most preferably, the polymerizable compound comprising a vinyl amide is N-vinyl caprolactam, as it provides particularly good ink curability and adhesion of the cured ink layer to the recording medium, especially when N-vinyl caprolactam is present in the radiation curable inkjet ink in an amount of 8.0 wt. -%, preferably of at least 10.0 wt. -%, most preferably of at least 15 wt. -%, based on the total weight of the radiation curable inkjet ink.
The polymerizable compounds including vinyl ethers or vinyl amides may be used alone or in combination of one or more polymerizable compounds including vinyl ethers or vinyl amides.
Other polymerizable Compounds
The radiation curable inkjet ink of the present invention may comprise other polymerizable compounds than the polymerizable compound comprising a vinyl ether group or a vinyl amide group. Any monomer and oligomer capable of free radical polymerization can be used in the radiation curable inkjet ink. The monomers and oligomers may have varying degrees of polymerizable functionality, and mixtures including combinations of mono-, di-, tri-, and higher polymerizable functionality monomers may be used. The viscosity of the radiation curable inkjet ink can be adjusted by varying the ratio between the monomers.
In order to minimize bad smell and health risks, the monomers and oligomers used are preferably purified compounds which contain no or hardly any impurities, more particularly no toxic or carcinogenic impurities. The impurities are generally derived compounds obtained during the synthesis of the polymerizable compound. Purification methods are well known to those skilled in the art of making monomers and oligomers. However, it may sometimes be desirable to add certain compounds to the pure polymerizable compound in harmless amounts, for example, polymerization inhibitors or stabilizers.
Particularly preferred monomers and oligomers are those listed in EP 1911814A (AGFA) [0106] to [0113 ].
Photoinitiator
The radiation curable inkjet ink preferably further comprises a photoinitiator. Photoinitiators require less energy to activate than the polymerizable compounds used to form the polymer. If the free radical inkjet ink does not contain an initiator, curing can be performed by electron beam curing.
More preferably, the radiation curable inkjet ink comprises a photoinitiating system comprising one or more photoinitiators and one or more co-initiators, rather than a single photoinitiator.
The photoinitiator in the curable inkjet ink may be a Norrish type I initiator or a Norrish type II initiator. Such photoinitiators are compounds that initiate the polymerization of monomers and oligomers by forming free radicals when exposed to actinic radiation. Norrish type I initiators are initiators that cleave upon excitation, generating an initiating free radical immediately. Norrish type II initiators are photoinitiators that are activated by actinic radiation and form free radicals by abstracting hydrogen from a second compound that becomes the actual initiating free radical. This second compound is known as a polymerization synergist or co-initiator. Both type I and type II photoinitiators can be used in the present invention, either alone or in combination.
Norrish type II photoinitiators
The radiation curable inkjet ink preferably comprises a Norrish type II photoinitiator comprising a photoinitiating moiety selected from the group consisting of a thioxanthone group and a benzophenone group. The Norrish type II photoinitiator containing a thioxanthone group is particularly preferred as it facilitates UV LED curing, especially for UV LEDs having an emission wavelength of 360nm or even 370 nm.
Suitable examples of Norrish type II photoinitiators containing a thioxanthone group include, but are not particularly limited to, thioxanthone; diethylthioxanthone, such as 2, 4-diethylthioxanthone; isopropylthioxanthones such as 2-isopropylthioxanthone and 4-isopropylthioxanthone; and chlorothioxanthones, such as 2-chlorothioxanthone.
A specific example of a commercially available Norrish type II photoinitiator containing thioxanthone groups is Speedcure from LAMBSON TM DETX (2, 4-diethylthioxanthone) and Speedcure TM ITX (2-isopropylthioxanthone) and Kayacure from Nippon Kayaku Co TM DETX-S (2, 4-diethylthioxanthone).
Suitable examples of Norrish type II photoinitiators containing a benzophenone group include, but are not particularly limited to, benzophenone; methyl benzophenone; methyl 2-benzoylbenzoate, phenylbenzophenones, such as 4-phenylbenzophenone; trimethylbenzophenone; bis (alkylamino) benzophenones; and 4- (dialkylamino) benzophenone.
A specific example of a commercially available Norrish type II photoinitiator containing a benzophenone group is Omnirad from IGM RESINS TM 4MBZ and Omnirad TM BP, Speedcure from LAMBSON TM PBZ and Speedcure TM 5040. The latter is a mixture of benzophenone and thioxanthone.
The Norrish type II photoinitiator comprising photoinitiating moieties selected from the group consisting of thioxanthone groups and benzophenone groups is preferably present in an amount of from 0.5 to 7.5 wt%, more preferably from 1 to 5 wt%, based on the total weight of the radiation curable inkjet ink. However, if the Norrish type II photoinitiator is a polymerizable or polymeric thioxanthone compound, the content based on the total weight of the radiation curable inkjet ink may be higher, preferably up to 25 wt%, more preferably up to 15 wt%.
Preferred examples of polymerizable Norrish type II photoinitiators comprising a photoinitiating moiety selected from a thioxanthone group or a benzophenone group are disclosed in EP 2161264 a (agfa), EP 2199273 a (agfa) and EP 2684876 a (agfa).
Preferred examples of polymeric Norrish type II photoinitiators comprising a photoinitiating moiety selected from a thioxanthone group or a benzophenone group are disclosed in EP 1616920 a (agfa) and EP 1616899 a (agfa).
Commercial examples of polymeric thioxanthones and benzophenones include Omnipol from IGM RESINS TM BP、Omnipol TM TX and Omnipol TM 2702。
Acylphosphine oxide and alpha-hydroxyketone photoinitiator
Aldehydes can also be formed from acylphosphine oxide photoinitiators and alpha-hydroxy ketone photoinitiators as photolytic byproducts upon UV exposure. Scheme 1 below shows how trimethyl benzoyl radicals are formed upon UV exposure, which upon extraction of hydrogen from a suitable hydrogen donor present in radiation curable inkjet inks, yield trimethyl benzaldehyde (trimesoyl benzaldehyde) with a characteristic almond odor. The phosphine oxide radical initiates the polymerization reaction of polymerizable compounds present in the radiation curable inkjet ink.
Scheme 1: aldehyde formation from 2,4, 6-trimethyldiphenylphosphine oxide
As an example of the formation of aldehydes from alpha-hydroxy ketone photoinitiators, scheme 2 is given, wherein benzaldehyde is formed from benzoyl radicals after extraction of hydrogen.
And (2) a flow scheme: aldehyde formation from 1-hydroxycyclohexyl phenyl ketones
Acylphosphine oxide photoinitiators are particularly advantageous for curability when UV curing is carried out using UV LEDs having a long wavelength of more than 360nm, especially when the acylphosphine oxide photoinitiators are further combined with Norrish type II photoinitiators containing thioxanthone groups.
Preferred examples of the acylphosphine oxide photoinitiator include, but are not particularly limited to, bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide, and bis- (2, 6-dimethoxybenzoyl) -2,4, 4-trimethylpentylphosphine oxide.
Preferred commercially available acylphosphine oxide photoinitiators include, but are not particularly limited to, Irgacure TM 819 (bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide) and Darocur TM TPO (2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide), both available from BASF; and Speedcure TPO-L from LAMBSON ((2,4, 6-trimethylbenzoyl) ethyl phenylphosphonite).
The acylphosphine oxide photoinitiator is preferably present in an amount of from 3 to 15 wt%, more preferably from 5 to 13 wt%, and still more preferably from 6 to 10 wt%, based on the total weight of the radiation curable inkjet ink.
Examples of the α -hydroxyketone photoinitiator include, but are not particularly limited to, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) -phenyl ] 2-hydroxy-2-methyl-1-propan-1-one.
Examples of commercially available alpha-hydroxyketone photoinitiators include, but are not particularly limited to, Darocur from BASF TM 1173、Irgacure TM 184 and Irgacure TM 127 Speedcure from LAMBSON TM 2022 and Omnirad from IGM RESINS TM 4817。
The content of the alpha-hydroxyketone is preferably from 1 to 10 wt%, more preferably from 2 to 8 wt%, and still more preferably from 3 to 6 wt%, based on the total weight of the radiation curable inkjet ink.
In preferred embodiments, one or more acyl groups of the acylphosphine oxide photoinitiator or alpha-hydroxyketone photoinitiator are attached to a polymer or polymerizable group. The acyl group of the photoinitiators of schemes 1 and 2 forms a benzoyl group which upon hydrogen abstraction forms an aldehyde, resulting in a noticeable odor of the cured ink layer. When these aldehydes are attached to the polymer or polymerizable group, they become diffusion hindered and odor is minimized because they remain almost completely in the cured ink layer.
Suitable polymeric acylphosphine oxide photoinitiators are disclosed in EP 2960303A (FUJFILM).
A preferred example of a polymerizable acylphosphine oxide photoinitiator is the compound UREA-2 given in our example 3 below.
An example of a suitable polymeric alpha-hydroxyketone photoinitiator is available as Esacure ™ KIP150 from IGM RESINS.
Suitable polymerizable alpha-hydroxyketone photoinitiators are disclosed in US 4922004 (MERCK), for example 4- (2-acryloyloxyethoxy) -phenyl 2-acryloyloxy-2-propyl ketone prepared in example 3.
Other photoinitiators
Instead of or in addition to the Norrish type II photoinitiator comprising a photoinitiating moiety selected from a thioxanthone group or a benzophenone group, the acylphosphine oxide photoinitiator and the alpha-hydroxy ketone photoinitiator, the radiation curable inkjet ink may comprise further free radical photoinitiators. Other suitable Photoinitiators may for example be selected from those disclosed in "CRIVELLO, J.V., et al, Photocouplers for Free radial Cationic and Anionic Photopolymerization. 2nd edition. Edited by BRADLEY, G.London, UK: John Wiley and Sons Ltd, 1998. p.287-294".
Preferred additional photoinitiators are selected from the group consisting of benzoin ethers, benzil ketals, α -dialkoxyacetophenones, α -aminoalkylphenones, acylphosphine sulfides, α -halo ketones, α -halo sulfones, α -halo phenylglyoxylates, 1, 2-diketones and anthraquinones.
Co-initiators
To further improve the photosensitivity, the radiation curable inks may additionally comprise coinitiators, also known as polymerization synergists, usually amine synergists being used.
Suitable examples of amine synergists can be divided into three groups:
1) aliphatic tertiary amines such as methyldiethanolamine, dimethylethanolamine, triethanolamine, triethylamine and N-methylmorpholine;
(2) aromatic amines such as amyl p-dimethylaminobenzoate, 2-n-butoxyethyl 4- (dimethylamino) benzoate, 2- (dimethylamino) ethyl benzoate, ethyl 4- (dimethylamino) benzoate and 2-ethylhexyl 4- (dimethylamino) benzoate; and
(3) (meth) acrylate amines, such as dialkylaminoalkyl (meth) acrylates (e.g., diethylaminoethyl acrylate) or N-morpholinoalkyl- (meth) acrylates (e.g., N-morpholinoethyl acrylate).
A preferred group of effective amine synergists are alkanolamines. However, these compounds are also very susceptible to hydrolysis, leading to the formation of aldehydes, such as formaldehyde. An example of such a hydrolysis scheme is given in scheme 3 below.
And (3) a flow scheme: formation of aldehydes from alkanolamines
It was found that radiation curable inkjet inks may contain high amounts of alkanolamines, such as Sartomer from ARKEMA TM CN3755, e.g.If the singlet oxygen quencher according to the present invention is present, the generation of formaldehyde is effectively minimized.
In another aspect of the present invention, a preferred embodiment of the radiation curable inkjet ink comprises a) at least 3 wt% of a compound comprising an alkanolamine group based on the total weight of the radiation curable inkjet ink; and
b) singlet oxygen quenchers according to formula (I):
Wherein
The integer N =0 if X represents S, or N =1 if X represents N;
r1 and R2 represent independently selected C 1 -C 6 Alkyl groups of alkyl groups; r3 represents C 1 -C 6 Alkyl or a-L4- (C = O) -O-R5 group;
r4 represents C 1 -C 6 Alkyl or a-L5- (C = O) -O-R6 group;
l1 to L5 represent alkylene groups independently selected from ethylene, propylene and butylene groups; and
r5 and R6 represent independently selected C 1 -C 6 Alkyl groups of the alkyl groups.
The alkanolamine co-initiator is preferably defined as an amine synergist according to formula (a-1):
R 5 And R 6 Independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, and substituted or unsubstituted aralkyl; r 7 And R 8 Independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, and substituted or unsubstituted aralkyl; and wherein R 5 To R 8 Any of which may represent the atoms necessary to form a five to eight membered ring. In a particularly preferred embodiment, R 7 And R 8 Represents hydrogen.
In a further preferred embodiment, the amine synergist is a compound according to formula (a-2):
wherein R is 9 And R 10 Independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl and substituted or unsubstituted aralkyl.
Preferred amine synergists including alkanolamine groups include Triethanolamine (TEA) and Methyldiethanolamine (MDEA).
Preferred examples of amine synergists including alkanolamine groups are given in table 1, but are not limited thereto
TABLE 2
In a most preferred embodiment, the amine synergist comprises an alkanolamine group
Are polymeric or oligomeric coinitiators obtained by condensation of 2-hydroxy-ethylamine with difunctional acrylates or methacrylates, particularly preferably difunctional acrylates. A particularly preferred commercially available amine synergist comprising alkanolamine groups is Sartomer containing compound AA-1 TM CN3755：
In a preferred embodiment, the amine synergist comprising an alkanolamine group or a dimethylbenzoate group is present in an amount of from 4 to 20 wt. -%, more preferably from 5 to 15 wt. -%, most preferably from 6 to 10 wt. -%, based on the total weight of the radiation curable inkjet ink. In such a range, excellent curability is obtained.
For certain ink-jet applications, the one or more co-primers are for safety reasonsHair agents are diffusion hindered. The diffusion hindered coinitiator is preferably selected from the group consisting of non-polymeric di-or multifunctional coinitiators, oligomeric or polymeric coinitiators and polymerizable coinitiators. More preferably, the diffusion hindered co-initiator is selected from the group consisting of a polymerization co-initiator and a polymerizable co-initiator. To minimize the effect on viscosity, it is most preferred that the diffusion hindered co-initiator is a polymerizable co-initiator having at least one (meth) acrylate group, more preferably having at least one acrylate group. A preferred compound containing an alkanolamine group is the acrylate amine polymerization synergist Sartomer from ARKEMA TM CN3755。
The radiation curable inkjet ink preferably includes a polymerizable or polymeric tertiary amine co-initiator. Preferred diffusion hindered coinitiators are the polymerizable coinitiators disclosed in paragraphs [0088] and [0097] of EP2053101A (AGFA).
Preferred diffusion hindered coinitiators include polymeric coinitiators having a dendritic polymeric structure, more preferably a hyperbranched polymeric structure. Preferred hyperbranched polymeric co-initiators are those disclosed in US 2006014848 a (agfa).
The radiation curable inkjet ink preferably comprises a (diffusion hindered) co-initiator in an amount of 0.1 to 50 wt%, more preferably in an amount of 0.5 to 25 wt%, most preferably in an amount of 1 to 15 wt% of the total weight of the inkjet ink.
Colouring agent
The radiation curable inkjet ink may comprise a colorant. The colorant used in the inkjet ink may be a dye, a pigment, or a combination thereof. Organic and/or inorganic pigments are preferred because of their migration fastness and superior photobleaching characteristics compared to dyes.
The pigment can be black, white, cyan, magenta, yellow, red, orange, violet, blue, green, brown, mixtures thereof, and the like. Such color Pigments may be selected from those disclosed in "HERBST, Willy, et al, Industrial Organic Pigments, Production, Properties, applications, 3rd edition, Wiley-VCH, 2004. ISBN 3527305769".
Particularly preferred pigments are c.i. pigment yellow 1,3, 10, 12, 13, 14, 17, 55, 65, 73, 74, 75, 83, 93, 97, 109, 111, 120, 128, 138, 139, 150, 151, 154, 155, 175, 180, 181, 185, 194 and 213.
Particularly preferred pigments are c.i. pigment red 17, 22, 23, 41, 48:1, 48:2, 49:1, 49:2, 52:1, 57:1, 88, 112, 122, 144, 146, 149, 170, 175, 176, 184, 185, 188, 202, 206, 207, 210, 216, 221, 248, 251, 254, 255, 264, 266, 270 and 272.
Particularly preferred pigments are c.i. pigment violet 19, 23, 32 and 37.
Particularly preferred pigments are c.i. pigment blue 15:1, 15:2, 15:3, 15:4, 15:6, 16, 56, 61 and (bridged) aluminium phthalocyanine pigments.
Particularly preferred pigments are c.i. pigment orange 5, 13, 16, 34, 40, 43, 59, 66, 67, 69, 71 and 73.
Particularly preferred pigments are c.i. pigment green 7 and 36.
Particularly preferred pigments are c.i. pigment brown 6 and 7.
Suitable pigments include the mixed crystals of the particularly preferred pigments described above. Mixed crystals are also known as solid solutions. For example, under certain conditions, different quinacridones are mixed with each other to form solid solutions, in contrast to both the physical mixture of the compounds and the compounds themselves. In solid solution, the molecules of the composition enter the same crystal lattice, usually but not always the crystal lattice of one of the components. The X-ray diffraction pattern of the resulting crystalline solid is characteristic of the solid and can be clearly distinguished from the pattern of a physical mixture of the same components in the same proportions. In such physical mixtures, the X-ray pattern of each component can be unique, and the disappearance of many lines is one of the criteria for forming a solid solution. An example of a commercial product is Cinqasia from BASF AG TM Magenta RT-355-D。
Carbon black is preferred as the black pigment. Suitable Black pigments include Carbon blacks such as pigment Black 7 (e.g., Carbon Black MA 8) ® From MITSUBISHI CHEMICAL), Regal ® 400R，Mogul ® L，Elftex ® 320 from CABOT Co., or Carbon Black FW18, Special Black 250, Special Black 350, Special Black 550，Printex ® 25，Printex ® 35，Printex ® 55，Printex ® 90，Printex ® 150T from DEGUSSA. In a preferred embodiment, the carbon black pigment used is a pigment having less than 0.15% of a toluene extractable fraction using the method described in Council of Europe published, resolution AP (89) 1, part III, 13, 1989, month 13, paragraph 5.
Mixtures of pigments may also be prepared. For example, in some inkjet ink applications, a neutral black inkjet ink is preferred and may be obtained, for example, by mixing a black pigment and a cyan pigment into the ink. Pigments may also be combined to expand the color gamut of the ink set. The inkjet ink set may also include one or more spot colors. Silver and gold are often desirable colors to make a product more attractive by giving the product a unique appearance.
Non-organic pigments may also be present in the ink. Suitable pigments are c.i. pigment metals 1,2 and 3. Illustrative examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron (III) oxide, cadmium red, ultramarine blue, prussian blue, chromium oxide green, cobalt green, amber, titanium black, and synthetic iron black. However, care should be taken to prevent migration and extraction of heavy metals in food applications. Pigments containing heavy metals selected from the group consisting of arsenic, lead, mercury and cadmium are preferably not used. In a more preferred embodiment, no inorganic pigment is used in the inkjet ink, other than the titanium oxide or calcium carbonate used in the optional white inkjet ink.
The pigment particles in the inkjet ink should be small enough to allow the ink to flow freely through the inkjet printing apparatus, especially at the nozzles. It is also desirable to use small particles to obtain maximum color intensity and slow sedimentation.
The number average pigment particle size is preferably between 0.050 and 1 μm, more preferably between 0.070 and 0.300. mu.m and particularly preferably between 0.080 and 0.200. mu.m. Most preferably, the number average pigment particle size is no greater than 0.150 μm. An average particle size of less than 0.050 μm is less desirable because of reduced light fastness, but primarily also because very small pigment particles or individual pigment molecules thereof can still be extracted in food packaging applications.
The number average pigment Particle size of the pigment particles is preferably determined using a Brookhaven Instruments Particle Sizer BI90plus based on the principle of dynamic light scattering. The ink is then diluted, for example with ethyl acetate, to a pigment concentration of 0.002% by weight. The measurement of BI90plus was set as: run 5 times, 23 ℃, angle 90 °, wavelength 635nm, and pattern = correction function.
In the case of white inkjet inks, it is preferred to use pigments having a refractive index greater than 1.60, preferably greater than 2.00, more preferably greater than 2.50, most preferably greater than 2.60. The white pigments may be used alone or in combination.
Titanium dioxide is preferably used for the pigment, having a refractive index of greater than 1.60. Titanium oxide exists in the crystalline forms of anatase type, rutile type and brookite type. Anatase is relatively low in density and easily ground into fine particles, while rutile is relatively high in refractive index and exhibits high hiding power. Any of these may be used in the present invention. It is preferable to utilize the properties as much as possible and to select them according to their uses. Excellent dispersion stability, ink storage stability and jettability can be achieved using anatase type having a low density and a small particle size. At least two different crystalline forms may be used in combination. The combined use of anatase type and rutile type exhibiting high tinting strength can reduce the total amount of titanium oxide, resulting in improved storage stability and ejection properties of the ink.
For the surface treatment of titanium oxide, water treatment or vapor phase treatment is applied, and an alumina-silica treating agent is generally used. Untreated, alumina-treated or alumina-silica treated titanium oxides may be used.
The number average particle size of the titanium oxide or other white pigment is preferably from 50 to 500nm, more preferably from 150 to 400nm, most preferably from 200 to 350 nm. When the average diameter is less than 50nm, sufficient hiding power cannot be obtained, and when the average diameter exceeds 500nm, the storage ability and ejection suitability of the ink tend to be lowered. The determination of the number average particle size is best carried out by photon correlation spectroscopy at a wavelength of 633nm using a 4mW HeNe laser against a diluted sample of the pigmented inkjet ink. Used ofA suitable particle size analyzer is Malvern available from Goffin-Meyvis TM nano-S. The sample can be prepared, for example, by adding one drop of ink to a cuvette containing 1.5mL of ethyl acetate and mixing until a homogeneous sample is obtained. The measured particle size is the average of 3 consecutive measurements consisting of 6 20 second runs.
Generally, the pigments are stabilized in the dispersion medium by dispersants such as polymeric dispersants or surfactants. However, the surface of the pigment may be modified to obtain a so-called "self-dispersing" or "self-dispersing" pigment, i.e. a pigment that is dispersible in the dispersion medium without a dispersant.
The pigment is preferably used in the pigment dispersion used for preparing the inkjet ink in an amount of 10 to 40% by weight, more preferably 15 to 30% by weight, based on the total weight of the pigment dispersion. In a colour inkjet ink, the pigment is preferably present in an amount of from 0.1 to 20 wt%, preferably from 1 to 13 wt%, based on the total weight of the inkjet ink.
Dispersing agent
The radiation curable inkjet ink may further comprise a dispersant to further improve the pigment dispersing properties. Examples of the dispersant include, but are not particularly limited to, dispersants generally used for preparing pigment dispersions, such as polymer dispersants.
Typical polymeric dispersants are copolymers of two monomers, but may contain three, four, five or more monomers. The nature of the polymeric dispersant depends on the nature of the monomers and their distribution in the polymer. The copolymer dispersant preferably has the following polymer composition:
statistical polymerization of monomers (e.g., monomers a and B polymerized to ABBAABAB);
alternating polymerized monomers (e.g., monomers a and B polymerized to ABABABAB);
gradient (tapered) polymerized monomers (e.g., monomers a and B polymerized to aaabaababbabbb);
block copolymers (e.g., monomers a and B polymerized into AAAAABBBBBB), where the block length of each block (2, 3, 4, 5 or even more) is important for the dispersability of the polymeric dispersant;
a graft copolymer (the graft copolymer consists of a polymeric backbone and polymeric side chains attached to the backbone); and mixed forms of these polymers, such as block gradient copolymers.
Suitable polymeric dispersants are listed in the "dispersants" section of EP 1911814 a (agfa graphics), more specifically [0064] to [0070] and [0074] to [0077], incorporated herein by specific reference.
The number average molecular weight Mn of the polymeric dispersant is preferably between 500 and 30000, more preferably between 1500 and 10000.
The polymeric dispersant preferably has a weight average molecular weight Mw of less than 100,000, more preferably less than 50,000, most preferably less than 30,000.
The polymeric dispersant preferably has a polydispersity PD of less than 2, more preferably less than 1.75, and most preferably less than 1.5.
Commercial examples of polymeric dispersants are as follows:
DISPERBYK TM a dispersant, available from BYK CHEMIE GMBH;
SOLSPERSE TM a dispersant obtainable from LUBRIZOL;
TEGO TM DISPERS TM dispersant, available from EVONIK;
EDAPLAN TM a dispersant from M Ü NZING chemiee;
ETHACRYL TM a dispersant from LYONDELL;
GANEX TM a dispersant from ISP;
DISPEX TM and EFKA TM Dispersants from BASF;
DISPONER TM a dispersant from DEUCHEM.
Particularly preferred polymeric dispersants include Solsperse TM A dispersant from LUBRIZOL; efka TM Dispersants from BASF; disperbyk TM A dispersant from BYK CHEMIE GMBH; and Ajisper TM Dispersant, available from Ajinomoto Fine-TECHNO Co. A particularly preferred dispersant is Solsperse TM 32000. 35000 and 39000 dispersants from LUBRIZOL.
The dispersing agent may be used alone or in combination of two or more thereof.
The polymeric dispersant is preferably used in an amount of from 2 to 600 wt%, more preferably from 5 to 200 wt%, most preferably from 50 to 90 wt%, based on the weight of the pigment.
Dispersion synergist
Dispersion builders generally consist of an anionic portion and a cationic portion. The anionic portion of the dispersion synergist shows some molecular similarity to the colour pigment, while the cationic portion of the dispersion synergist consists of one or more protons and/or cations to compensate the charge of the anionic portion of the dispersion synergist.
The amount of dispersion synergist added is preferably less than the polymeric dispersant. The ratio of polymeric dispersant/dispersion synergist depends on the pigment and should be determined experimentally. Typically the ratio of weight percent of polymeric dispersant/weight percent of dispersion synergist is selected between 2:1 and 100:1, preferably between 2:1 and 20: 1.
Suitable commercially available dispersion synergists include Solsperse from LUBRIZOL TM 5000 and Solsperse TM 22000。
Particularly preferred pigments for the magenta ink used are diketopyrrolopyrrole pigments or quinacridone pigments. Suitable dispersion synergists include those disclosed in EP 1790698 a (agfa graphics), EP 1790696 a (agfa graphics), WO 2007/060255 (AGFA GRAPHICS) and EP 1790695 a (agfa graphics).
In dispersing c.i. pigment blue 15:3, a sulfonated copper phthalocyanine dispersion synergist is used, for example Solsperse from LUBRIZOL TM 5000 is preferable.
Suitable dispersion synergists for yellow inkjet inks include those disclosed in EP 1790697 a (agfa graphics).
Polymerization inhibitor
The radiation curable inkjet ink may further comprise a polymerization inhibitor. Due to the fact that the ink contains a polymerization inhibitor, the polymerization reaction before curing can be prevented.
Suitable polymerization inhibitors include phenolic antioxidants, hindered amine light stabilizers, phosphorus-type antioxidants, benzoquinones, hydroquinones, and derivatives thereof, such as hydroquinone monomethyl ether commonly used in (meth) acrylate monomers.
Examples of phenolic polymerization inhibitors include, but are not limited to, p-methoxyphenol, cresol, t-butylcatechol, di-t-butyl-p-cresol, hydroquinone monomethyl ether, α -naphthol, 3, 5-di-t-butyl-4-hydroxytoluene, 2, 6-di-t-butyl-4-methylphenol, 2' -methylene-bis (4-methyl-6-t-butylphenol), 2' -methylene-bis (4-ethyl-6-butylphenol), 4' -thio-bis (3-methyl-6-t-butylphenol), and pyrogallol.
Suitable commercial inhibitors are, for example, Sumilizer TM GA-80、Sumilizer TM GM and Sumilizer TM GS, produced by Sumitomo Chemical co. ltd.; genorad TM 16、Genorad TM 18 and Genorad TM 20, from Rahn AG; irgastab TM UV10 and Irgastab TM UV22、Tinuvin TM 460 and CGS20 from Ciba Specialty Chemicals; floorstab TM UV series (UV-1, UV-2, UV-5 and UV-8) from Kromachem Ltd; additol TM S series (S100, S110, S120 and S130) from Cytec Surface Specialties.
A preferred polymerization inhibitor is Irgastab from BASF TM UV 10. Other examples of polymerization inhibitors include TEMPO, TEMPOL and AI cupferron.
The polymerization inhibitor may be used alone or in combination of two or more thereof.
In a preferred embodiment, the polymerization inhibitor is a mixture of different types of polymerization inhibitors. Preferred polymerization inhibitors are mixtures of oxygen radical based polymerization inhibitors, phenol based polymerization inhibitors and amine based polymerization inhibitors. Suitable examples are given in EP 2851402 a (fujifilm).
The addition amount of the polymerization inhibitor is preferably 200 to 20,000ppm with respect to the total amount of the inkjet ink.
Surface active agent
The radiation curable inkjet ink may comprise at least one surfactant. The surfactant may be an anionic, cationic, nonionic or zwitterionic surfactant and is preferably added in a total amount of less than 3 wt% based on the total weight of the ink, in particular less than 1.5 wt% based on the total weight of the radiation curable inkjet ink, to prevent foaming of the ink in its container. The surfactant is preferably present in an amount of 0.05 to 1.5 wt%, more preferably 0.10 to 1.0 wt%, based on the total weight of the radiation curable inkjet ink.
Preferred surfactants are selected from the group consisting of fluorosurfactants (e.g., fluorinated hydrocarbons) and silicone surfactants. The silicone surfactant is preferably a siloxane and may be alkoxylated, polyester-modified, polyether-modified hydroxy-functional, amine-modified, epoxy-modified and other modifications or combinations thereof. Preferred silicones are polymeric, such as polydimethylsiloxane.
Preferred commercial silicone surfactants include BYK from BYK Chemie TM 333, and BYK TM UV3510。
In a preferred embodiment, the surfactant is a polymerizable compound.
Preferred polymerizable silicone surfactants include (meth) acrylate silicone surfactants. Most preferably, the (meth) acrylate silicone surfactant is an acrylate silicone surfactant because acrylates are more reactive than methacrylates.
In a preferred embodiment, the (meth) acrylate silicone surfactant is a polyether modified (meth) acrylate polydimethylsiloxane or a polyester modified (meth) acrylate polydimethylsiloxane.
Preferred commercially available (meth) acrylate silicone surfactants include Ebecryl TM 350, silicone diacrylate from Cytec; polyether modified acrylate polydimethylsiloxane BYK TM UV3500 and BYK TM UV3530 polyester modified acrylate polydimethylsiloxane BYK TM UV3570, allIs produced by BYK Chemie; tego TM Rad 2100、Tego TM Rad 2200N、Tego TM Rad 2250N、Tego TM Rad 2300、Tego TM Rad 2500、Tego TM Rad 2600 and Tego TM Rad 2700、Tego TM RC711 from EVONIK; silaplane TM FM7711、Silaplane TM FM7721、Silaplane TM FM7731、Silaplane TM FM0711、Silaplane TM FM0721、Silaplane TM FM0725、Silaplane TM TM0701、Silaplane TM TM0701T, both manufactured by CHISSO Corporation; and DMS-R05, DMS-R11, DMS-R18, DMS-R22, DMS-R31, DMS-U21, DBE-U22, SIB1400, RMS-044, RMS-033, RMS-083, UMS-182, UMS-992, UCS-052, RTT-1011 and UTT-1012, all produced by GELEST Inc.
Preparation of radiation curable inkjet inks
The preparation of pigmented radiation curable inkjet inks is well known to the person skilled in the art. Preferred preparation processes are disclosed in paragraphs [0076] to [0085] of WO2011/069943 (AGFA).
Ink jet printing method
The inkjet printing method according to a preferred embodiment of the present invention includes the steps of: jetting one or more radiation curable inks as described above onto a substrate; and UV curing the one or more curable inks on the substrate.
The UV curing is preferably carried out by UV LEDs emitting at wavelengths greater than 360nm, preferably greater than 370 nm.
Radiation curable inkjet inks are jetted from one or more print heads that eject small droplets through a nozzle in a controlled manner onto a packaging substrate that is moving relative to the print head.
A preferred print head for use in an inkjet printing system is a piezoelectric head. Piezoelectric inkjet printing is based on the motion of a piezoelectric ceramic transducer when a voltage is applied to it. Application of a voltage changes the shape of the piezoelectric ceramic transducer in the printhead, creating a void, which is then filled with an inkjet ink or liquid. When the voltage is removed again, the ceramic expands to its original shape, ejecting a drop of ink from the print head.
The preferred piezoelectric print head is a so-called push-mode type piezoelectric print head, which has a relatively large piezoelectric element and is also capable of ejecting ink droplets of high viscosity. Such a print head is available from RICOH as GEN5s print head.
A preferred piezoelectric print head is a so-called through-flow piezoelectric drop-on-demand print head. Such a printhead is available as the CF1ou printhead from TOSHIBA TEC. Through-flow print heads are preferred as they improve the reliability of food safe ink jet printing.
Inkjet print heads typically scan back and forth laterally across the surface of a moving ink receiver. Typically the inkjet print head does not print on the way back. Bi-directional printing is preferred to achieve high area throughput.
Another preferred printing method is by a "single pass printing process", which can be performed by using a page wide inkjet print head or a plurality of staggered inkjet print heads covering the entire width of the ink receiver surface. In a single pass printing process, the inkjet print head is typically held stationary while the ink receiver surface is transported under the inkjet print head.
In a particularly preferred embodiment, the inkjet printing of the UV curable inkjet ink is performed in a multi-pass printing mode. Multipass printing is a technique for reducing banding in inkjet printing. The ink dots tend to clump together while still in the liquid state due to surface tension. This is called coalescence. To print high quality images, it is important to print a single dot. But to obtain a fully saturated color, the dots must overlap to completely cover the substrate. Coalescence can be largely avoided by printing only a portion of the image data to avoid simultaneous printing of adjacent dots during each print cycle. Furthermore, by avoiding all horizontal adjacency, the lateral speed of the printing mechanism can be increased to at most twice the rated print speed of the print head. In a preferred embodiment, the number of passes used is from 2 to 6 passes, more preferably not more than 4 passes.
The advantage of using a multi-pass printing mode is that the UV curable inkjet ink is cured in a continuous pass, rather than a single pass, which requires a curing device with high UV output. The life of the print head for multi-pass printing is also longer. While in single pass printing one side shooter is sufficient to replace the entire print head, in multi-pass printing side shooters can even fail. In addition, multi-pass printers are typically much lower in cost, especially for wide format substrates.
Curing
The radiation curable inkjet ink is preferably cured by ultraviolet radiation.
In inkjet printing, the UV curing device may be arranged in combination with the print head of the inkjet printer, running with it, so that the UV curable inkjet ink is exposed to curing radiation shortly after jetting.
In such an arrangement, it may be difficult to provide a sufficiently small source of UV radiation connected to and travelling with the print head. Thus, a stationary radiation source may be employed, which is static, for example a curing UV light source, connected to the radiation source by a flexible radiation conducting means, such as a fiber optic bundle or an internally reflective flexible tube.
Alternatively, actinic radiation may be supplied to the radiation head from a stationary source by an arrangement of mirrors, including mirrors on the radiation head.
The radiation source, which is arranged to not move with the print head, may also be an elongate radiation source which extends transversely across the surface of the ink receiver to be cured and adjacent the transverse path of the print head so that subsequent image lines formed by the print head pass beneath the radiation source in steps or in succession.
Any source of ultraviolet light, provided that a portion of the emitted light is absorbed by the photoinitiator or photoinitiator system, may be used as a radiation source, such as high or low pressure mercury lamps, cold cathode tubes, black light lamps, ultraviolet LEDs, ultraviolet lasers, and flash lamps. Among these, preferred light sources are light sources exhibiting a relatively long wavelength UV contribution with a dominant wavelength of 300-400 nm. In particular, UV-a light sources are preferred because their light scattering is reduced, resulting in more efficient internal curing.
UV radiation is generally divided into UV-A, UV-B and UV-C, as follows:
UV-A: 400nm to 320nm
UV-B: 320nm to 290nm
UV-C: 290nm to 100 nm.
Further, the image may be cured using two light sources of different wavelengths or illumination, either sequentially or simultaneously. For example, the first UV source may be selected to be UV-C rich, particularly in the range of 260nm to 200 nm. The second UV source may then be rich in UV-a, such as a gallium doped lamp, or a different lamp with both high UV-a and UV-B. The use of two UV sources has been found to have advantages such as fast cure speed and high cure levels.
In a particularly preferred embodiment, the UV curing is carried out using UV LEDs emitting at wavelengths above 370 nm.
To facilitate curing, inkjet printers typically include one or more oxygen consuming units. The oxygen consuming unit is filled with a layer of nitrogen or other relatively inert gas (e.g. CO) 2 ) With adjustable position and adjustable inert gas concentration to reduce the oxygen concentration in the curing environment. Residual oxygen levels are typically kept as low as 200ppm, but are typically in the range of 200ppm to 1200 ppm.
Method for producing interior decoration product
A method of producing an interior trim article comprising the steps of:
a) inkjet printing one or more UV curable inkjet inks according to the present invention as described above on a substrate; and b) UV curing the one or more UV curable inkjet inks. The UV curing is preferably carried out using UV LEDs with emission wavelengths greater than 360 nm.
In a preferred embodiment of the production method, the upholstery item is selected from the group consisting of a decorative sheet, furniture, wallpaper, a door, a leather item and a textile fabric.
Interior decoration product
Interior trim articles comprising a cured layer of one or more radiation curable inkjet inks according to the present invention are preferably selected from the group consisting of decorative panels, furniture, wallpaper, door leather articles and textile fabrics.
The decorative panel may be a simple panel, such as a glass or metal panel, but may also be a decorative laminate panel selected from a floor panel, a ceiling panel and a wall panel. Decorative laminate panels are made by ink jet printing on decorative paper or a thermoplastic substrate, which is then hot-pressed with at least one protective layer into a decorative laminate.
The thermoplastic substrate is preferably based on a material selected from the group consisting of polyvinyl chloride (PVC), polypropylene (PP), Polyethylene (PE), polyethylene terephthalate (PET) and Thermoplastic Polyurethane (TPU), and combinations thereof. PVC-based decorative laminates are also known on the market as LVT (luxury vinyl tiles).
Before hot pressing, the decorative paper is impregnated with a thermosetting resin, for example a melamine based thermosetting resin. Such decorative laminate panels are known as wood-based decorative laminate panels.
Industrial applicability
The radiation curable inkjet inks of the present invention can be advantageously used in other inkjet applications besides the production of upholstery articles. There is no practical limitation on the type of inkjet application, but radiation curable inkjet inks may also be advantageously used in packaging, for example for packaging of foodstuffs, cosmetics and pharmaceuticals.
The term "packaging for food, cosmetic or pharmaceutical products" is to be understood in its broadest sense as comprising packaging for a substance to be ingested or administered by humans or animals. The food may be solid or liquid, for example, it also includes beverages such as beer, soda, milk, vegetable oils, yogurt, and the like. There is no limitation on the shape of the package for food, cosmetics or medicines. For example, the food package may be in the shape of a cup, bottle, pouch, box, can, carton, wrapper, and the like. For cosmetic reasons, cosmetics comprise different solid or liquid products, which can be applied to human hair, for example shampoos. Pharmaceutical packaging includes, for example, blister packs, plastic bottles, pouches and bags for Intravenous (IV) therapy.
Of course, the composition of the radiation curable inkjet ink is preferably adjusted to a so-called low migration ink composition for food safety and health reasons.
In a preferred embodiment, the radiation curable inkjet ink includes a monomer including at least one acrylate group and at least one ethylenically unsaturated polymerizable group selected from the group consisting of allyl ethers, allyl esters, allyl carbonates, vinyl ethers, vinyl esters, vinyl carbonates, fumarates and maleates. Preferred examples of such monomers are disclosed in EP 2053103 a (agfa).
The radiation curable inkjet ink preferably contains a vinyl ether acrylate monomer represented by the formula (VA-1) disclosed above.
The radiation curable inkjet ink most preferably includes VEEA as the vinyl ether acrylate monomer.
In a preferred embodiment, the vinyl ether (meth) acrylate monomer is present in the free radical curable inkjet ink in an amount of from 20 wt% to 90 wt%, more preferably from 25 wt% to 80 wt%, most preferably from 30 wt% to 70 wt%, all based on the total weight of the radiation curable inkjet ink.
In a particularly preferred embodiment, the polymerizable composition of the radiation curable inkjet ink consists essentially of: a)25 to 100% by weight of one or more polymerizable compounds A having at least one acrylate group and at least one vinyl ether group; b)0 to 55% by weight of one or more polymerizable compounds B selected from the group consisting of monofunctional acrylates and difunctional acrylates; and C)0 to 55 wt% of one or more polymerizable compounds C selected from the group consisting of trifunctional acrylates, tetrafunctional acrylates, pentafunctional acrylates and hexafunctional acrylates, with the proviso that if the weight percentage of compound B >24 wt%, the weight percentage of compound C >1 wt%; wherein all weight percents of A, B and C are based on the total weight of the polymerizable composition; and with the proviso that if the radiation curable inkjet ink does not contain an initiator, at least one polymerizable compound B or C is present in the polymerizable composition. If no initiator is present, the radiation curable inkjet ink may be cured by electron beam curing.
Examples
Material
Unless otherwise indicated, all materials used in the following examples are readily available from standard sources such as Aldrich Chemical co. The water used is demineralized water.
PIG-M is a mixed crystal of quinacridones and can be used as Cinqasia TM Magenta D4500J was obtained from BASF.
SYN is a dispersion synergist according to formula (a):
Synthesized in the same manner as synergist QAD-3 described in example 1 of WO2007/060254(AGFA GRAPHICS).
DB162 is for polymeric dispersant Disperbyk available from BYK CHEMIE GMBH TM 162, wherein the solvent mixture of 2-methoxy-1-methylethyl acetate, xylene and n-butyl acetate is removed. The polymeric dispersant is a polyester-polyurethane dispersant based on caprolactone and toluene diisocyanate, having an amine value of 13mg KOH/g, an Mn of about 4,425, and an Mw of about 6,270.
DPGDA is dipropylene glycol diacrylate as a Laromer TM DPGDA was obtained from BASF.
G1122 is a monofunctional urethane acrylate, useful as Genomer TM 1122 from RAHN.
TBCH is 4-tert-butylcyclohexyl acrylate available from ARKEMA under the trade name Sartomer TM CD217 was obtained.
VEEA is 2- (2' -vinyloxyethoxy) ethyl acrylate, a difunctional monomer available from NIPPON SHOKUBA, Japan.
NVC is N-vinyl caprolactam available from BASF BELGIUM, NV.
ITX is Darocur TM ITX, an isomeric mixture of 2-and 4-isopropylthioxanthone from BASF.
TPO-L is ethyl phenyl (2,4, 6-trimethylbenzoyl) phosphonite available from IGM Resins BV as Omnirad TM TPO-L.
BAPO is a bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide photoinitiator available from BASF as Irgacure TM 819 to a pharmaceutically acceptable carrier.
CN3755 is an acrylate amine synergist useful as Sartomer TM CN3755 was obtained from ARKEMA.
GAB is a polymeric 4-dimethylaminobenzoic acid derivative available as GENOPOL from RAHN TM AB 2.
Stabi I is a monomeric carbodiimide, useful as Stabaxol TM I is obtained from LANXESS AG.
Stabi L is a monomeric carbodiimide, useful as Stabaxol TM L is obtained from LANXESS AG.
Stabi S was synthesized as follows:
sodium ethoxide was freshly prepared by adding 49.6g (2.16mol) of sodium in portions to 840ml of ethanol. The mixture was stirred for three hours. 183g (1.08mol) of 2- (diethylamino) ethanethiol hydrochloride are added and the mixture is stirred for 30 minutes. A solution of 150g of dimesylated polyethylene glycol 200 in 400ml of ethanol was added. The reaction mixture was heated to reflux for 4 hours. The reaction mixture was cooled to room temperature, the precipitated salt was removed by filtration, and the solvent was evaporated under reduced pressure. The residue is dissolved in 600ml of dichloromethane and carefully extracted 3 times with 240ml of 10% hydrochloric acid. The aqueous phase is neutralized with 30w% sodium hydroxide solution and extracted 3 times with 360ml of dichloromethane. The combined dichloromethane fractions were taken over Na 2 SO 4 Dried and evaporated under reduced pressure. The crude polymer was purified by preparative column chromatography on silica gel using dichloromethane/methanol/ammonia 90/9/1 as eluent. 125 g of Stabi S were isolated.
INHIB is a polymerization inhibitor forming mixture having a composition according to table 3.
TABLE 3
| Components | By weight% |
| VEEA | 82.4 |
| p-methoxyphenol | 4.0 |
| Butylated Hydroxytoluene (BHT) | 10.0 |
| Cupferron TM AL | 3.6 |
Cupferron TM AL is N-nitrosophenylhydroxylamine aluminum from WAKO CHEMICALS LTD.
C7500 is organosilicon surfactant, and can be used as Silwet TM L7500 is from OSI SPECIALIES BENELUX NV.
Measuring method
1. Formaldehyde emission
Anapurina for UV curable inks TM H2050i LED ink jet system at 25cm 2 On aluminum substrate was printed to 100% ink coverage and UV cured. Then 5 strips of 1x5cm were cut from the printed aluminum sample and placed into 20ml gas chromatography vials. The closed vial was heated at 100 ℃ for 60 minutes. Immediately after heating, hot air was collected and added to a cartridge (Xposure Aldehyde Sampler, from WATERS) containing acidified 2, 4-dinitrophenylhydrazine coated silica. An additional 180ml of pure air was added to the cartridge through the sample vial to ensure that all of the formaldehyde was loaded into the cartridge. The amount of formaldehyde was determined by HPLC-DAD from the reaction product formaldehyde, 2- (2, 4-dinitrophenyl) hydrazone eluted from the cartridgeAnd (4) determining the quantity. This content is determined according to a calibration curve established with a standard solution of formaldehyde, 2- (2, 4-dinitrophenyl) hydrazone.
2. Acetaldehyde discharge
Anapurina for UV curable inks TM H2050i LED ink jet system at 25cm 2 On aluminum substrates were printed to 100% ink coverage and UV cured. Then 5 strips of 1x5cm were cut from the printed aluminum sample and placed into 20ml gas chromatography vials. The closed vial was heated at 100 ℃ for 120 minutes. After cooling to 25 ℃, the air in the closed vial was collected and added to a cartridge (Xposure Aldehyde Sampler, from WATERS) containing acidified 2, 4-dinitrophenylhydrazine coated silica. An additional 180ml of pure air was added to the cartridge through the sample vial to ensure that all acetaldehyde was loaded into the cartridge. The amount of acetaldehyde was determined by HPLC-DAD from the amount of acetaldehyde, 2- (2, 4-dinitrophenyl) hydrazone, which is a reaction product eluted from the cartridge. This content is determined according to a calibration curve established with a standard solution of acetaldehyde, 2- (2, 4-dinitrophenyl) hydrazone.
3. Average particle size
The average particle size of the pigment particles in the pigment dispersion was determined by photon correlation spectroscopy using a particle size analyzer PSS aw-388 available from NICOMP.
The sample was prepared by adding one drop of the dispersion to a cuvette containing 1.5mL of ethyl acetate and mixing until a homogeneous sample was obtained. The measured particle size is the average of 3 consecutive measurements consisting of 6 20 second runs.
4. Surface tension
The static surface tension of the UV-curable ink was measured after 60 seconds at 25 ℃ with a Delta 8 Multipi 1A tensiometer from KRIBON.
5. Viscosity of the oil
Viscosity of UV curable compositions Rotovisco from HAAKE was used TM RV1 viscometer at 45 ℃ and 1,000s -1 Is measured at a shear rate of (c).
6.LC-MS
In AmaZon TM Some hydrolysis stabilisers were analysed on an SL mass spectrometer (supplied by Brucker Daltonics) using an Alltech Altima C18 (150 mm x 3.2 mm) column at a temperature of 40 ℃ and a flow rate of 0.5ml/min using ESI as the ionisation technique. Elution was performed using a gradient as follows:
eluent A: 10mmol ammonium acetate/methanol 9/1 in water
Eluent B: 10mmol ammonium acetate in methanol
TABLE 4
| Elution time (min) | % of eluent B |
| 0 | 0 |
| 8 | 100 |
| 15 | Stop |
Example 1
This example illustrates the synthesis of singlet oxygen quenchers HS-1 to HS-4.
Synthesis of singlet oxygen quencher HS-1
The synthesis of ethyl 3- [2- (diethylamino) ethyl- (3-ethoxy-3-oxo-propyl) amino ] propionate (HS-1) proceeds according to the following reaction scheme:
51.06 g (0.51 mol) of ethyl acrylate were dissolved in 38g of ethanol. The solution was cooled to 0 ℃. A solution of 23.24 g (0.2mol) of N, N-diethylethylenediamine in 38g of ethanol was added. The reaction was allowed to continue at 0 ℃ for 45 minutes. The mixture was heated to 21 ℃ and the reaction was allowed to continue at 21 ℃ for 24 hours. An additional 5g (0.05mol) of ethyl acrylate in 5g of ethanol was added and the reaction was allowed to continue for an additional 48 hours. The solvent and excess ethyl acrylate were removed under reduced pressure and crude HS-1 was used without further purification. HS-1 was analyzed using LC MS. HS-1 consists of 96.5% of the target structure, contaminated with 3.5% of the monomethyl ester analog, due to transesterification with methanol present in ethanol.
Synthesis of singlet oxygen quencher HS-2
The synthesis of ethyl 3- [3- [ bis (3-ethoxy-3-oxo-propyl) amino ] propyl- (3-ethoxy-3-oxo-propyl) amino ] propionate (HS-2) proceeds according to the following reaction scheme:
100.12 g (1 mol) of ethyl acrylate were dissolved in 62g of ethanol. The reaction mixture was cooled to 0 ℃. A solution of 14.83 g (0.2mol) of 1, 3-propanediamine in 33g of ethanol was added. The reaction was allowed to continue at 0 ℃ for one hour. The reaction mixture was warmed to room temperature and the reaction was allowed to proceed at room temperature for 20 hours. The reaction mixture was further heated to 35 ℃ and the reaction was allowed to continue at 35 ℃ for 6 hours. The solvent and excess ethyl acrylate were removed under reduced pressure and crude HS-2 was used without further purification. HS-2 was analyzed using LC MS. HS-2 consists of 72% of the target structure, 25% of compounds in which 1, 3-propanediamine has reacted only 3 times with ethyl acrylate. Monomethyl ester analogs of both compounds were also found in the mixture due to transesterification with methanol present in ethanol.
Synthesis of singlet oxygen quencher HS-3
The synthesis of ethyl 3- [ (3-ethoxy-3-oxo-propyl) - [2- (3-ethoxy-3-oxo-propyl) sulfanylethyl ] amino ] propionate (HS-3) proceeds according to the following reaction scheme:
under nitrogen atmosphere, 10.8 g (0.14 mol) cysteamine was added to 34g ethanol, and the suspension was cooled to 1 ℃. A solution of 47.52 g (0.47 mol) of ethyl acrylate in 34g of ethanol was added. The mixture was stirred at 1 ℃ for 45 minutes. The mixture was further stirred under a continuous nitrogen flow for 24 hours. Reaction conversion was monitored using GC. A solution of 11g (0.11mol) ethyl acrylate in 11g ethanol was added and the reaction was continued under a continuous stream of nitrogen for a further 24 hours. An additional 22g (0.22mol) of ethyl acrylate in 22g of ethanol were added and the reaction was continued under a continuous stream of nitrogen for a further 24 hours. The reaction was not yet complete. The nitrogen flow was stopped to avoid evaporation of the ethyl acrylate. A further 20g (0.22mol) of ethyl acrylate in 20g of ethanol were added and the reaction was continued at 35 ℃ for 48 hours. The solvent and excess ethyl acrylate were removed under reduced pressure and crude HS-3 was used without further purification. HS-3 was analyzed using LC MS. The crude product consisted of 70% of the target structure and 30% of the compound in which cysteamine reacted only twice with ethyl acrylate.
Synthesis of singlet oxygen quencher HS-4
The synthesis of ethyl 3- [2- [ bis (3-ethoxy-3-oxo-propyl) amino ] ethyl- (3-ethoxy-3-oxo-propyl) amino ] propionate (HS-4) proceeds according to the following reaction scheme:
85.1g (0.85mol) of ethyl acrylate were dissolved in 38g of ethanol. The solution was cooled to 0 ℃ and a continuous stream of nitrogen was placed over the reaction mixture. A solution of 12.02g (0.2mol) of ethylenediamine in 38g of ethanol was added over 30 minutes. The reaction was allowed to continue at 1 ℃ for 45 minutes and then stirred at room temperature for 24 hours. An additional 15g (0.15mol) of ethyl acrylate in 15g of ethanol were added and the reaction was continued for 30 hours at 21 ℃ under a continuous stream of nitrogen. An additional 28g (0.28mol) of ethyl acrylate in 28g of ethanol was added and the reaction was continued under a continuous stream of nitrogen at 21 ℃ for an additional 24 hours. The nitrogen flow was stopped and the mixture was heated to 35 ℃ for another 48 hours. The solvent and excess ethyl acrylate were removed under reduced pressure and crude HS-4 was used without further purification. HS-4 was analyzed using LC MS. HS-4 consists of 73% of the target structure, 10% of the compound in which ethylenediamine has reacted only 3 times with ethyl acrylate. Monomethyl ester analogs of both compounds were also found in the mixture due to transesterification with methanol present in ethanol.
Example 2
This example illustrates the reduction of aldehyde emissions from a UV cured layer of a radiation curable inkjet ink according to the present invention while maintaining good shelf life.
Preparation of a magenta Dispersion DISP-M
By using DISPERLUX from DISPERLUX s.a.r.l., Luxembourg TM The disperser mixes the components according to table 5 for 30 minutes to prepare the dispersion. The dispersion was then milled using a Bachofen DYNOMILL ECM mill filled with 0.4mm yttrium stabilized zirconia beads ("high attrition resistant zirconia milling media", from TOSOH Co.). The mixture was circulated over the mill for 2 hours. After milling, the concentrated pigment dispersion was discharged into a vessel through a 1 micron filter.
TABLE 5
| Components | By weight% |
| PIG-M | 16.94 |
| SYN | 0.90 |
| DB162 | 16.94 |
| INHIB | 1.00 |
| DPGDA | 64.22 |
Preparation of radiation curable inkjet inks
Comparative UV-curable inkjet inks C-1 to C-6 according to table 6 and inventive UV-curable inkjet inks I-1 to I-8 according to table 7 were then prepared using the magenta pigment dispersion DISP-M prepared above. The weight% is based on the total weight of the inkjet ink.
TABLE 6
| Weight percent: | C-1 | C-2 | C-3 | C-4 | C-5 | C-6 |
| DISP-M | 26.56 | 26.56 | 26.56 | 26.56 | 26.56 | 26.56 |
| DPGDA | 3.40 | 3.40 | 3.40 | 3.40 | 3.40 | 3.40 |
| G1122 | 6.71 | 6.36 | 6.11 | 5.76 | 3.76 | 3.76 |
| TBCH | 18.90 | 17.91 | 17.23 | 16.24 | 18.90 | 18.90 |
| VEEA | 30.69 | 29.08 | 27.97 | 26.36 | 28.69 | 28.69 |
| ITX | --- | 2.95 | --- | 2.95 | 2.95 | 2.95 |
| TPO-L | 4.50 | 4.50 | 4.50 | 4.50 | 4.50 | 4.50 |
| BAPO | 3.50 | 3.50 | 3.50 | 3.50 | 3.50 | 3.50 |
| CN3755 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 |
| Stabi S | --- | --- | 5.00 | 5.00 | --- | --- |
| Stabi I | --- | --- | --- | --- | 2.00 | --- |
| Stabi L | --- | --- | --- | --- | --- | 2.00 |
| INHIB | 0.74 | 0.74 | 0.74 | 0.74 | 0.74 | 0.74 |
| C7500 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 |
TABLE 7
| Weight percent: | I-1 | I-2 | I-3 | I-4 | I-5 | I-6 | I-7 | I-8 |
| DISP-M | 26.56 | 26.56 | 26.56 | 26.56 | 26.56 | 26.56 | 26.56 | 26.56 |
| DPGDA | 3.40 | 3.40 | 3.40 | 3.40 | 3.40 | 3.40 | 3.40 | 3.40 |
| G1122 | 6.11 | 5.76 | 6.11 | 5.76 | 6.11 | 5.76 | 6.11 | 5.76 |
| TBCH | 17.23 | 16.24 | 17.23 | 16.24 | 17.23 | 16.24 | 17.23 | 16.24 |
| VEEA | 27.97 | 26.36 | 27.97 | 26.36 | 27.97 | 26.36 | 27.97 | 26.36 |
| ITX | --- | 2.95 | --- | 2.95 | --- | 2.95 | --- | 2.95 |
| TPO L | 4.50 | 4.50 | 4.50 | 4.50 | 4.50 | 4.50 | 4.50 | 4.50 |
| BAPO | 3.50 | 3.50 | 3.50 | 3.50 | 3.50 | 3.50 | 3.50 | 3.50 |
| CN3755 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 | 4.00 |
| HS-1 | 5.00 | 5.00 | --- | --- | --- | --- | --- | --- |
| HS-2 | --- | --- | 5.00 | 5.00 | --- | --- | --- | --- |
| HS-3 | --- | --- | --- | --- | 5.00 | 5.00 | --- | --- |
| HS-4 | --- | --- | --- | --- | --- | --- | 5.00 | 5.00 |
| INHIB | 0.74 | 0.74 | 0.74 | 0.74 | 0.74 | 0.74 | 0.74 | 0.74 |
| C7500 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 |
evaluation and results
All inkjet inks were found to have a surface tension of 29 mN/m. Viscosity and average particle size were measured directly after preparation and% increase was calculated by measuring viscosity and average particle size again after aging treatment at 60 ℃ for 14 days.
TABLE 8
As should be clear from Table 8, only the comparative ink-jet inks C-3 and C-4 exhibited poor shelf life.
TABLE 9
As can be seen from Table 9, good shelf-life stability was obtained only for inkjet inks I-1 to I-8, while there was no or reduced aldehyde emission from their UV cured layers. Furthermore, it can be seen that the Norrish type II photoinitiator ITX increases the aldehyde emission.
Claims (15)
1. A radiation curable inkjet ink comprising
A polymerizable compound comprising a vinyl ether group or a vinyl amide group;
optionally, an amine synergist comprising an alkanolamine group or a dimethylbenzoate group;
optionally, a Norrish type II photoinitiator comprising a photoinitiating moiety selected from the group consisting of a thioxanthone group, a benzophenone group, a ketocoumarin group, and a camphorquinone group; and
a singlet oxygen quencher according to formula (I):
wherein
The integer N =0 if X represents S, or N =1 if X represents N;
r1 and R2 represent independently selected C 1 -C 6 Alkyl groups of alkyl groups;
r3 represents C 1 -C 6 Alkyl or a-L4- (C = O) -O-R5 group;
r4 represents C 1 -C 6 Alkyl or a-L5- (C = O) -O-R6 group;
l1 to L5 represent alkylene groups independently selected from ethylene, propylene and butylene groups; and
r5 and R6 represent independently selected C 1 -C 6 Alkyl groups of the alkyl groups.
2. The radiation curable inkjet ink according to claim 1 wherein L1 to L5 represent ethylene groups.
3. The radiation curable inkjet ink according to claim 1 wherein R1 to R6 represent ethyl groups.
4. The radiation curable inkjet ink according to claim 1, wherein the singlet oxygen quencher is selected from the group consisting of:
5. the radiation curable inkjet ink according to claim 1,
wherein the radiation curable inkjet ink comprises a Norrish type II photoinitiator comprising a photoinitiating moiety selected from a thioxanthone group and a benzophenone group.
6. The radiation curable inkjet ink according to claim 1,
wherein the polymerizable compound containing a vinyl ether group is a vinyl ether acrylate compound, or the polymerizable compound containing a vinyl amide group is N-vinylcaprolactam.
7. The radiation curable inkjet ink according to claim 6 wherein the vinyl ether acrylate compound is 2- (2-vinyloxyethoxy) ethyl acrylate.
8. The radiation curable inkjet ink according to claim 1, further comprising an acylphosphine oxide photoinitiator or an alpha-hydroxy ketone photoinitiator.
9. The radiation curable inkjet ink according to claim 8, wherein one or more acyl groups of the acylphosphine oxide photoinitiator or alpha-hydroxyketone photoinitiator are attached to a polymer or polymerizable group.
10. A radiation curable inkjet ink set comprising one or more radiation curable inkjet inks according to any one of claims 1 to 9.
11. An interior trim article comprising a cured layer of one or more radiation curable inkjet inks according to any one of claims 1 to 9, wherein the interior trim article is selected from the group consisting of decorative panels, furniture, wallpaper, doors, leather articles and textile fabrics.
12. An inkjet printing method comprising the steps of:
-printing one or more radiation curable inks according to any one of claims 1 to 9 on a substrate; and
-subjecting the one or more curable inks on the substrate to UV curing.
13. The inkjet printing method according to claim 12, wherein the UV curing is performed by a UV LED having an emission wavelength of more than 360 nm.
14. A method of producing an interior decoration article comprising the inkjet printing method according to claim 12 or 13.
15. The method of claim 14, wherein the interior product is selected from the group consisting of decorative panels, furniture, wallpaper, doors, leather products, and textile fabrics.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP19153567.3 | 2019-01-24 | ||
| EP19153567.3A EP3686251B1 (en) | 2019-01-24 | 2019-01-24 | Radiation curable inkjet inks for interior decoration |
| PCT/EP2020/051569 WO2020152243A1 (en) | 2019-01-24 | 2020-01-23 | Radiation curable inkjet inks for interior decoration |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113348216A CN113348216A (en) | 2021-09-03 |
| CN113348216B true CN113348216B (en) | 2022-08-02 |
Family
ID=65234425
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202080010695.5A Active CN113348216B (en) | 2019-01-24 | 2020-01-23 | Radiation curable inkjet inks for interior decoration |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20220119656A1 (en) |
| EP (1) | EP3686251B1 (en) |
| CN (1) | CN113348216B (en) |
| WO (1) | WO2020152243A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11845874B2 (en) * | 2019-01-24 | 2023-12-19 | Agfa Nv | Radiation curable inkjet inks for interior decoration |
| JP7435121B2 (en) * | 2020-03-25 | 2024-02-21 | セイコーエプソン株式会社 | Radiation-curable inkjet composition and inkjet method |
| CN113969144B (en) * | 2021-10-12 | 2023-07-04 | 浙江巨化技术中心有限公司 | Composition and application thereof in liquid coolant and liquid cooling system |
| NL2032127B1 (en) | 2022-06-10 | 2023-12-18 | Trespa Int Bv | A method for manufacturing a monomer dispersion pigment concentrate. |
| WO2024017881A1 (en) | 2022-07-19 | 2024-01-25 | Agfa-Gevaert Nv | A curable inkjet composition for the manufacturing of printed circuit boards |
| WO2024017926A1 (en) | 2022-07-19 | 2024-01-25 | Agfa-Gevaert Nv | A curable inkjet composition for the manufacturing of printed circuit boards |
| WO2024017864A1 (en) | 2022-07-19 | 2024-01-25 | Agfa-Gevaert Nv | A curable inkjet composition for the manufacturing of printed circuit boards |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6096801A (en) * | 1997-06-06 | 2000-08-01 | Ciba Specialty Chemicals Corporation | Pigment compositions |
| EP0981590B1 (en) * | 1997-05-16 | 2004-01-28 | Chevron Phillips Chemical Company LP | Photoinitiators and oxygen scavenging compositions |
| CN104039898A (en) * | 2011-12-16 | 2014-09-10 | 爱克发印艺公司 | Curable Liquids And Inkjet Inks For Food Packaging Applications |
| WO2016011116A1 (en) * | 2014-07-18 | 2016-01-21 | Lubrizol Advanced Materials, Inc. | Matting or texturing effects through tung oil in uv coatings |
| CN105573056A (en) * | 2015-12-18 | 2016-05-11 | 杭州福斯特光伏材料股份有限公司 | Light-sensing dry film resist |
| WO2017211587A1 (en) * | 2016-06-07 | 2017-12-14 | Agfa Graphics Nv | Photoinitiators and curable compositions |
Family Cites Families (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3534645A1 (en) | 1985-09-28 | 1987-04-02 | Merck Patent Gmbh | COPOLYMERIZABLE PHOTOINITIATORS |
| US20030083396A1 (en) | 2001-07-23 | 2003-05-01 | Ylitalo Caroline M. | Ink jet ink compositions |
| US7396861B2 (en) | 2004-07-15 | 2008-07-08 | Agfa Graphics Nv | Radiation curable compositions |
| EP1616920B1 (en) | 2004-07-15 | 2008-02-20 | Agfa Graphics N.V. | Novel polymeric initiators |
| EP1616899B2 (en) | 2004-07-15 | 2014-07-02 | Agfa Graphics N.V. | Novel photoreactive polymers |
| EP1790698B1 (en) | 2005-11-28 | 2010-04-14 | Agfa Graphics N.V. | Non-aqueous diketopyrrolo-pyrrole pigment dispersions using dispersion synergists |
| PL1790696T3 (en) | 2005-11-28 | 2013-09-30 | Agfa Nv | Non-aqueous pigment dispersions containing specific dispersion synergists |
| EP1790697B1 (en) | 2005-11-28 | 2012-01-25 | Agfa Graphics N.V. | Non-aqueous pigment dispersions containing specific dispersion synergists |
| DE602005012843D1 (en) | 2005-11-28 | 2009-04-02 | Agfa Graphics Nv | Non-aqueous quinacridone dispersions using dispersion synergists |
| PL1911814T5 (en) | 2006-10-11 | 2023-12-11 | Agfa Nv | Methods for preparing curable pigment inkjet ink sets |
| EP2053103B1 (en) | 2007-10-24 | 2010-10-06 | Agfa Graphics N.V. | Curable liquids and inks for toys and food packaging applications |
| PL2325270T3 (en) | 2007-10-24 | 2013-02-28 | Agfa Nv | Curable liquids and inks for toys and food packaging applications |
| CN101177475A (en) * | 2007-11-02 | 2008-05-14 | 湖南大学 | Method for synthesizing branch polyurethane capable of being ultraviolet solidified |
| EP2161264B1 (en) | 2008-09-09 | 2019-11-27 | Agfa Nv | Polymerizable photoinitiators and radiation curable compositions |
| CN101381477B (en) * | 2008-10-15 | 2011-04-27 | 天津大学 | Hindered amine light stabilizer and synthetic method thereof |
| EP2199273B1 (en) | 2008-12-18 | 2018-02-21 | Agfa Nv | Polymerizable photoinitiators and radiation curable compositions |
| WO2011069943A1 (en) | 2009-12-07 | 2011-06-16 | Agfa-Gevaert | Uv-led curable compositions and inks |
| JP5697617B2 (en) | 2012-02-09 | 2015-04-08 | 富士フイルム株式会社 | Ink composition for ink jet recording, ink jet recording method, and printed matter |
| EP2684876B1 (en) | 2012-07-10 | 2016-09-14 | Agfa Graphics N.V. | Polymerizable thioxanthones |
| JP6016768B2 (en) | 2013-02-21 | 2016-10-26 | 富士フイルム株式会社 | Ink composition, ink jet recording method, and polymer initiator |
| US20170152389A1 (en) * | 2015-11-27 | 2017-06-01 | Océ-Technologies B.V. | Uv curable gelling ink formulation with low wax migration in cured state |
-
2019
- 2019-01-24 EP EP19153567.3A patent/EP3686251B1/en active Active
-
2020
- 2020-01-23 WO PCT/EP2020/051569 patent/WO2020152243A1/en active Application Filing
- 2020-01-23 US US17/425,188 patent/US20220119656A1/en active Pending
- 2020-01-23 CN CN202080010695.5A patent/CN113348216B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0981590B1 (en) * | 1997-05-16 | 2004-01-28 | Chevron Phillips Chemical Company LP | Photoinitiators and oxygen scavenging compositions |
| US6096801A (en) * | 1997-06-06 | 2000-08-01 | Ciba Specialty Chemicals Corporation | Pigment compositions |
| CN104039898A (en) * | 2011-12-16 | 2014-09-10 | 爱克发印艺公司 | Curable Liquids And Inkjet Inks For Food Packaging Applications |
| WO2016011116A1 (en) * | 2014-07-18 | 2016-01-21 | Lubrizol Advanced Materials, Inc. | Matting or texturing effects through tung oil in uv coatings |
| CN105573056A (en) * | 2015-12-18 | 2016-05-11 | 杭州福斯特光伏材料股份有限公司 | Light-sensing dry film resist |
| WO2017211587A1 (en) * | 2016-06-07 | 2017-12-14 | Agfa Graphics Nv | Photoinitiators and curable compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3686251A1 (en) | 2020-07-29 |
| CN113348216A (en) | 2021-09-03 |
| WO2020152243A1 (en) | 2020-07-30 |
| EP3686251B1 (en) | 2021-11-17 |
| US20220119656A1 (en) | 2022-04-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113348216B (en) | Radiation curable inkjet inks for interior decoration | |
| CN109071979B (en) | Acylphosphine oxide photoinitiators | |
| US8389769B2 (en) | Polymerizable type II photoinitiators and curable compositions | |
| EP3046976B1 (en) | Radiation curable compositions for food packaging | |
| CN113302244B (en) | Radiation curable inkjet inks for interior decoration | |
| CN112334551B (en) | Acylphosphine oxide initiators | |
| CN109219644B (en) | Photoinitiator and curable composition | |
| CN114729211A (en) | Radiation curable inkjet ink set | |
| US20230416547A1 (en) | UV Curable Inkjet Inks and Inkjet Printing Methods |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |